Hybrid supported metallogen catalyst, method for preparing olefin polymer by using same, and olefin polymer having improved melt strength

Abstract

The invention relates to: a hybrid supported metallocene catalyst includes at least one first metallocene compound among the compounds represented by chemical formula 1, at least one second metallocene compound among the compounds represented by chemical formula 2 and a cocatalyst compound; a method for preparing an ethylene-α-olefin copolymer, comprising polymerizing olefin monomers in the presence thereof; and an ethylene-α-olefin copolymer having improved melt strength.

The invention claimed is: 
     
       1. A hybrid metallocene-supported catalyst, comprising:
 a carrier; 
 at least one first metallocene compound supported in the carrier, among compounds represented by Chemical Formula 1; 
 at least one second metallocene compound supported in the carrier, among compounds represented by Chemical Formula 2; and 
 a co-catalyst compound supported in the carrier: 
 
       
         
           
           
               
               
           
         
       
       in Chemical Formula 1, in *-MX 2 —*, M is any one of titanium (Ti), zirconium (Zr), and hafnium (Hf), X is one of halogen, an alkyl group of  C1-10 , and an alkenyl group of C 2-10 , and R 1 —*, R 2 —*, R 3 —*, R 4 —*, R 5 —*, R 6 —*, R 7 —*, R 8 —*, R 9 —*, R 10 —* are each independently one of H—*, an alkyl group of C 2-10 , a cycloalkyl group of C 3-6 , and an aryl group of C 6-14 , 
       
         
           
           
               
               
           
         
       
       in Chemical Formula 2, in *-MX 2 —*, M is any one of titanium (Ti), zirconium (Zr), and hafnium (Hf), X is any one of halogen, an alkyl group of  C1-10 , and an alkenyl group of C 2-10 , Q is any one of carbon (C), silicon (Si), germanium (Ge), and tin (Sn), R 1 —*, R 2 —*, R 3 —*, R 4 —*, R 5 —*, R 6 —*, R 7 —*, R 8 —*, R 9 —*, R 10 —*, R 11 —*, and R 12 —* are each independently one of *—H—, an alkyl group of C 2-10 , a cycloalkyl group of C 3-6 , and an aryl group of C 6-14 , and R 13 —* and R 14 —* are each independently an alkyl group of C 1-10 ,
 wherein a sum of an amount of the first metallocene compound to be supported and an amount of the second metallocene compound to be supported is 0.5 parts by weight to 3.0 parts by weight based on 1 g of the carrier, and 
 an amount of the co-catalyst compound to be supported is 20 parts by weight to 30 parts by weight based on 1 g of the carrier. 
 
     
     
       2. The hybrid metallocene-supported catalyst of  claim 1 ,
 wherein, in Chemical Formula 1, among Rm-*s (m is 1 to 10), two adjacent R n —* and R n+1 —* (n is 1 to 9) form 
 i) an unsubstituted single or multiple ring compound of C 3-15  with an alkyl group of C 1-4 , 
 ii) a substituted single or multiple ring compound of C 3-15  by alkyl group of C 1-4 , and Rm-*s other than R n —* and R n+1 —* are each independently one of H—*, an alkyl group of C 2-10 , a cycloalkyl group of C 3-6 , and an aryl group of C 6-14 . 
 
     
     
       3. The hybrid metallocene-supported catalyst of  claim 1 ,
 wherein, in Chemical Formula 2, among Rm-*s (m is 1 to 12), two adjacent R n —* and R n+1 —* (n is 1 to 9) form 
 i) an unsubstituted or multiple ring compound of C 3-15  with an alkyl group of C 1-4 , or 
 ii) a substituted single or multiple ring compound of C 3-15  by alkyl group of C 1-4 , and Rm-*s other than R n —* and R n+1 —* are each independently one of *—H—, an alkyl group of C 2-10 , a cycloalkyl group of C 3-6 , and an aryl group of C 6-14 . 
 
     
     
       4. The hybrid metallocene-supported catalyst of  claim 1 ,
 wherein the co-catalyst compound is at least one of at least one first co-catalyst compound among compounds represented by Chemical Formula 3 and at least one second co-catalyst compound among compounds represented by Chemical Formula 4: 
 
       
         
           
           
               
               
           
         
         in Chemical Formula 3, Ra-* is halogen-*, or a unsubstituted or substituted alkyl group of C 1-20 , cycloalkyl group of C 3-6 , or aryl group of C 6-14  with halogen, and n is an integer of 2 or more; and in Chemical Formula 4, D is aluminum or boron, Rb-* to Rd-* are the same as or different from each other and are each independently halogen-*, or a unsubstituted or substituted alkyl group of C 1-20 , cycloalkyl group of C 3-6 , or aryl group of C 6-14  with halogen. 
       
     
     
       5. A method of preparing an olefin polymer, comprising:
 polymerizing olefin monomers in the presence of the hybrid metallocene-supported catalyst according  claim 1 . 
 
     
     
       6. The method of  claim 5 ,
 wherein the olefin monomer is at least one selected from ethylene, propylene, 1-butene, 1-hexene, and 1-octene.